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C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES; PREPARATION OF CARBON BLACK; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS

C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black

C09C1/28—Compounds of silicon

C09C1/30—Silicic acid

C09C1/3081—Treatment with organo-silicon compounds

B—PERFORMING OPERATIONS; TRANSPORTING

B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL

B01D—SEPARATION

B01D19/00—Degasification of liquids

B01D19/02—Foam dispersion or prevention

B01D19/04—Foam dispersion or prevention by addition of chemical substances

B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance

B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms

C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES; PREPARATION OF CARBON BLACK; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS

C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black

C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers

C09K2200/02—Inorganic compounds

C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass

C09K2200/0247—Silica

Abstract

The invention relates to hydrophobicized precipitated silicas that possess an extremely high whiteness and extremely low moisture absorption. The hydrophobic precipitated silicas are prepared, inter alia, by coating with silicone oil and oxidative heat treatment.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a hydrophobic precipitated silica featuring extremely low water absorption, a high level of whiteness, and properties of low thickening in silicone rubber formulations with a high reinforcing action in the silicone vulcanizates.

2. Discussion of the Background

The treatment of finely divided solids, metal oxides, and silicates with organosilicon compounds, such as organopolysiloxanes, is known, for example, from DE 30 85 905. The heat treatment process this entails is carried out under an inert atmosphere of nitrogen. Additionally, hydrophobic silicates are known, for example, from DE 24 35 860, DE 22 42 728, and DE 25 13 608.

In these documents, hydrophilic silicates and precipitated silicas are hydrophobicized by reacting them with organosilicon compounds. Examples of hydrophobicizers used include organohalosilanes and organopolysiloxane compounds.

DE 26 28 975 and DE 27 29 244 describe preparing hydrophobic silicas by reacting a hydrophilic precipitated silica featuring low water absorbency with silicone oil or dimethyldichlorosilane, respectively. In the process according to DE 26 28 975, the reaction is carried out with the hydrophobicizer (silicone oil) being added to the dry precipitated silica; in the process according to DE 27 29 244, the hydrophobicizer (dimethyldichlorosilane) is introduced directly into the precipitated silica suspension. In both cases, the hydrophobicizing step is followed by heat treatment at elevated temperatures, specifically between 200 and 400° C.

A disadvantage of this process is that the precipitated silica thus hydrophobicized becomes discolored at the required process temperatures. The discoloration of this silica is particularly inconvenient when it is added to silicone formulations; that is, when these hydrophobic precipitated silicas are added to silicone rubber formulations or to defoamer mixtures based on silicone oil.

As a measure of the discoloration it is possible to use the value known as reflectance. In measuring the reflectance, the diffuse reflection power of a sample is investigated. The higher the diffuse reflection power of a sample, the higher its reflectance and thus the higher the whiteness of the sample.

Precipitated silicas generally have a reflectance of not more than 97%.

Discoloration occurs in particular when the precipitated silicas are strongly hydrophobicized; that is, have a high methanol wettability and high carbon loadings. It is precisely these properties, however, which are in many cases (in silicone rubber formulations, for example) desired.

A further disadvantage of the known processes is that only a limited amount of hydrophobicizer can be attached covalently to the silica. Particularly in silicone rubber formulations, however, high carbon loadings are desired, since they permit decisive improvements in the rheological properties, such as the thickening, i.e., low yield point and low viscosity, of the compounds.

As a measure of the thickening, it is possible to utilize the DBP number. The DBP number indicates the absorption capacity of a silica for DBP. The measurement technique shows the amount of dibutyl phthalate, in g, on a sample of 100 g, at which a massive increase in force in the compounder is observed.

It is also not possible to achieve high carbon loadings by using diorganodichlorosilanes, or hydrolysis products of diorganodichlorosilanes, or with corresponding diorganopolysiloxanes in excess to the silanol groups present, since the totality of the organosilicon compounds is no longer attached covalently to the silica. In hydrophobicized silicas for fractions of hydrophobicizing agent that has not been covalently attached, there is a risk that these molecules may have a marked mobility, which in many applications can be very detrimental (e.g., in silicone rubber applications for medical purposes or for articles that are safe in food contact, such as pacifiers, etc.).

A further disadvantage of the prior art processes is that the relatively low carbon contents of less than 3.1% lead to hydrophobic silicas which have a strong thickening action in silicone rubber formulations. DE 26 28 975 lists data on the testing of hydrophobic precipitated silica in silicone rubber formulations, in which the hydrophobic precipitated silica is used in increasing weight fractions. From these it is clear that, at a level of just 15% of hydrophobic silica in the rubber, the self-leveling properties of the silica disappear and that, at 20%, flowable compounds are no longer obtained. All tables clearly indicate that all of the mechanical properties are improved as the filler content goes up. It would therefore be desirable to prepare silicone rubber formulations which include high fractions of hydrophobic silicas, for improving the mechanical properties, but which at the same time are still flowable.

SUMMARY OF THE INVENTION

The present invention provides a precipitated silica that has a high covalently attached carbon loading, low water absorption, a low-thickening effect with good reinforcer properties in silicone rubber formulations, and a high level of whiteness. Ideally the present invention hydrophobicizes silicas in such a way that the reflectance of the original silica is retained.

It has surprisingly been found that a hydrophobic silica having the required properties can be obtained by distributing a polysiloxane on a hydrophilic silica with subsequent conditioning and oxidative heat treatment.

The present invention provides hydrophobic precipitated silicas characterized by the following properties:

carbon content

>3.1%;

methanol wettability

>60%;

reflectance

>94%;

BET/CTAB ratio

>1 and <3;

DBP absorption

<230 g/100 g;

BET surface area

50–110 m2/g;

CTAB surface area

>30 m2/g;

water vapor absorption at 30° C. and 30% relative

1.1 ± 0.2%; and

humidity

water vapor absorption at 30° C. and 70% relative

1.4 ± 0.3%.

humidity

The ranges of preference specified may be adjusted independently of one another.

The hydrophobic silicas of the invention may additionally, each independently of one another, be characterized by the following properties:

Sears number

<1.6;

pH

5–9;

water content

<2%;

conductivity

<150 μS; and

loss on ignition

>3%.

The conductivity may be below 100, 60, 30, or even 20 μS.

The present invention further provides a process for preparing hydrophobic precipitated silicas, comprising the following steps:

a) preparing a mixture of an organopolysiloxane derivative and a precipitated silica;

b) conditioning the mixture at from 10 to 150° C. for a period of from 0.5 to 72 h; and

c) conducting oxidative heat treatment at more than 300° C. with an oxidizing gas.

BRIEF DESCRIPTION OF THE DRAWINGS

The preferred embodiments of the invention will be described, with reference to the following figures, wherein:

FIG. 1 shows a steep methanol wettability curve representative of those obtained using the hydrophobic silicas of the present invention; and

contains no surfactants, emulsifiers or organic solvents which might lead to discoloration at elevated temperatures.

The process for preparing the silica of the invention makes it possible to obtain homogeneous distribution of the hydrophobicizer while avoiding the use of solvents (except for water), emulsifiers, surfactants or other surface-active molecular moieties in the hydrophobicizer, so that the resulting silica combines low-thickening properties with absence of discoloration.

The effective distribution of the hydrophobicizer and the high degree of hydrophobicization of the precipitated silica of the invention result in silicone rubber formulations, for example, with very low thickening, unimpaired even by prolonged storage, in conjunction with good mechanical and optical properties in the vulcanizates.

The silica of the invention is preferably prepared with a polysiloxane, so that after heat treatment its only organic radicals are methyl groups, this going hand in hand with a very high thermal load-bearing capacity (>300° C. with ingress of air does not lead to discolorations).

The process of the invention makes it possible to effect hydrophobicization particularly of silicas with a low silanol group density (the measure used for the amount of silanol groups is the Sears number, i.e., the alkali consumption of an acid-based titration; together with the BET surface area it is then possible to compare silanol group densities relatively) and to achieve a high whiteness (>94% reflectance) in the resulting silica of the invention.

The water absorption of the hydrophobic precipitated silica of the invention, which is very low for a precipitated silica, is made possible by the selection of a hydrophilic precipitated silica with a very low silanol group density and through very homogeneous hydrophobicization with organosilicon compounds. The measure used for the silanol group density is the Sears number in proportion to the BET surface area.

The reaction conditions employed in the process of the invention do not lead to carbonization and thus lead to virtually no discoloration. For this reason it is important that the hydrophilic base silica contains no organic impurities, since otherwise the discoloration increases. Since the cleavage products which form as a result of the heat treatment, and which are gaseous under the process conditions, may bring about a certain degree of discoloration even in an oxidizing atmosphere, it is important to remove these cleavage products from the product by means of a sufficient throughput of gas.

The use of liquid polysiloxane, preferably the polydimethylsiloxane of preferably 30–100 cSt, permits optimum distribution on the base silica. Under the oxidative reaction conditions, the polydimethylsiloxanes used are able to undergo resinification. This has the great advantage that the hydrophobicizer can be distributed on the silica in liquid form and then fixed. The amount of bound carbon can be greatly increased by the oxidative heat treatment.

Silicas of the invention exhibit steep methanol wettability curves. For example, FIG. 1 exhibits a steep wettability curve obtained using a silica of the present invention that shows that homogeneous hydrophobicization has taken place. In contrast, FIG. 2 shows the methanol wettability of conventional hydrophobic silicas heat-treated without the conditioning of the present invention.

High carbon loadings and high methanol wettabilities bring about decisive improvements in the properties of silicas in silicone rubber formulations. The further reduction in moisture absorbency permits vulcanizations at atmospheric pressure and at temperatures above 100° C. in silicone rubber formulations, since no disruptive vapor bubbles appear in the vulcanizate. The high carbon content silicas of the invention exhibit substantially improved Theological properties in silicone rubber formulations; that is, they have only a low thickening action, and exhibit low yield points. This low thickening action makes it possible to prepare flowable silicone rubber formulations that are filled with well above 20% of hydrophobic precipitated silica and yet can still be processed by injection molding. Additionally, the higher filling level leads to markedly improved mechanical properties in the vulcanizates.

The hydrophobic precipitated silica of the invention may therefore be used in the following applications.

1. As a Filler in Silicone Rubber Formulations

The silica of the invention can be used without further hydrophobicization in all types of silicone rubber. The low water absorption suppresses evolution of vapor in high temperature crosslinking systems such as LSR and HTV silicone rubber, and allows pore-free vulcanizates. The low DBP number leads to low compound viscosities, which can be used to advantage in LSR and RTV2 compounds. The compounds possess a high level of stability on storage: the phenomenon referred to as afterstiffening is suppressed. Because of the low moisture absorption, the silica of the invention can also be used in systems which cure by atmospheric humidity such as RTV1 compounds. The compounds likewise have a high level of stability on storage. Since the moisture content of the silica of the invention is greatly reduced, the unwanted hardening during storage is suppressed.

Because of the high whiteness of the silica, attractive white vulcanizates can be produced. The low water absorption of the silica results in low moisture absorption in the vulcanizates. This produces high electrical resistance and an increase in aging stability, especially at high temperatures. These properties are particularly useful in electrical insulators and in seals.

2. As a Defoamer Component

It is known, for example, from DE 28 29 906, U.S. Pat. No. 4,377,493, DE 34 11 759, U.S. Pat. No. 4,344, 858, and WO 95/05880 that hydrophobicized silicas can be used in defoamer formulations. Advantageous for high-level defoamer performance here are the high hydrophobicity and a high surface area, readily accessible even to relatively large molecules, of the silica of the invention. The high hydrophobicity of the silica of the invention, furthermore, ensures high alkali resistance and results in much higher service lives particularly in strongly alkaline media.

The high reflectances of the silicas of the invention ensure appealing defoamer formulations free from discoloration, particularly in formulations based on mineral oil and silicone oil.

3. As a Free-flow Agent

It is known (for example, from Degussa AG brochure series, Fällungskieselsäuren und Silikate (Precipitated silicas and silicates), 1984) that hydrophobicized silicas can be used as free-flow auxiliaries. Because of its low water absorption, the silica of the invention is particularly suitable as a free-flow auxiliary for substances that are sensitive to hydrolysis. Here again, the high reflectances of the silicas of the invention are an additional advantage.

The silica of the invention may also be used as a carrier substance, particularly for insecticides, as an insecticide per se, has an antiblocking auxiliary, or filler in silicone rubber mixtures which cure by atmospheric humidity.

The hydrophobic precipitated silicas of the invention are prepared in three steps.

First of all, a liquid polysiloxane derivative is initially distributed, physically, on the silica surface. Where this initial distribution is carried out in aqueous media, i.e., suspensions or silica with a water content of more than 70%, the silica is typically unstable. It must therefore be isolated quickly by filtration following the initial distribution, and/or subjected to accelerated drying (in a spin-flash drier or nozzle tower drier, for example). This conserves the distribution of the organopolysiloxane droplets on the silica and prevents separation into water, silicone oil, and silica.

Subsequently, in a controlled conditioning step—process step b)—the distribution of the hydrophobicizer is improved further and engagement of the polysiloxane derivative with the silica surface is achieved. This state of distribution is stable even in aqueous media. Following process step b), there is no longer any separation between the polysiloxane derivative and the silica. At carbon contents ≧3. 1, the conditioned silicas can be adjusted steplessly to a methanol wettability of up to 55%. The BET/CTAB ratio after this step is <1. The binding of the polysiloxane to the silica is thought to be a result of the formation of multiple hydrogen bonds between the siloxane bridges of the polysiloxane molecules and the silanol groups on the silica surface.

This is followed by a heat treatment in an oxidizing atmosphere, which suppresses discoloration phenomena, ensures covalent binding of the hydrophobicizing agent, and—probably as a result of the formation of gaseous cleavage products—increases further the distribution of the hydrophobicizer. Heat treated silicas, with a lower carbon content than the corresponding conditioned silica, have a higher methanol wettability. Heat treatment in an oxidizing atmosphere assists the resinification of the polysiloxanes, so that much larger amounts of hydrophobicizer can be anchored covalently on the silica. The BET/CTAB ratio has turned around and is now >1.

As the organopolysiloxane derivative it is possible to use all organosilanes or organohalosilanes that are commonly used to hydrophobicize precipitated silicas.

Step a) of the process of the invention can be conducted with the following variants.

A first variant of step a) is the addition of organopolysiloxane derivative to a precipitated silica having a water content of from 1.0 to 80% by weight, preferably from 20 to 60% by weight;

A second variant of step a) is the addition of the organopolysiloxane derivative to a dispersion of the precipitated silica, i.e., following precipitation of silicate with an acid, for example, using a Rhein-Hütte mixer or Kotthof-Mischsirene or Ultra-Turrax. This necessitates rapid filtration and/or accelerated drying (spin-flash drier, spray drier, nozzle tower) after the reaction.

A third variant of step a) is the addition of the organopolysiloxane derivative to a precipitated silica having a water content of from 70 to 99% by weight, with subsequent isolation of the solid from the water. Isolation can be effected by filtration, nozzle tower, spin-flash, or other short term drying. The higher the water content, the more quickly isolation should be carried out. Separation should be avoided.

A fourth variant of step a) is simultaneously supplying the precipitated silica or hydrous silica and the organopolysiloxane derivative to a spin-flash drier.

A fifth variant of step a) is mixing of dry precipitated silica with polysiloxane, in a Gericke mixer, for example.

An alternative possibility is first to prepare a masterbatch, i.e., a conditioned precipitated silica, obtained according to process steps a) and b), and to mix it with a (hydrophilic), hydrous precipitated silica (e.g., filtercake, silica suspension or silica dispersion).

The water content of the hydrophilic precipitated silica may vary within the ranges mentioned above.

The base silica may be coated in a mass ratio, for example, of from 1:1 to 1:3 with silicone oil, e.g, DOW CORNING (R) 200 FLUID 50 CS (50 mPas dimethylpolysiloxane terminated with trimethylsilyl groups, carbon content of approximately 33%) (step a)). The resulting powder is conditioned at a temperature of more than 100° C. for half an hour, for example. The conditioning (step b) here is carried out until the resulting material is wettable by water (methanol wettability <20; regarding the definition of methanol wettability see the measurement technique section) but which when introduced into water no longer exhibits any separation between silica and silicone oil (if step c) follows directly on from step b), a methanol wettability >20 is preferred). Mixing of this masterbatch, (e.g., 50% by weight silica and 50% silicone oil) with aqueous silica dispersions or silica suspensions produces stable mixtures in which the silicone oil no longer separates from the silica. The total mixture typically contains one part by weight of silicone oil, about 4–8 parts by weight of silica, and 20–60 parts by weight of water. In order to prepare such a suspension, for example, the masterbatch (e.g., 50% silica and 50% silicone oil) can be mixed thoroughly with about 10–16 times the amount of filtercake (solids content approximately 20%) and about 10–20 times the amount of additional water. The advantage of this procedure is that the water-wettable masterbatch (which contains up to 75% of hydrophobic organo polysiloxane) can be dispersed directly in silica precipitation suspensions or silica feeds, very finely and stably, without the need to use emulsifiers or surfactants. After such a mixture has been dried, or filtered and then dried, the organopolysiloxane-containing silica thus obtained can be conditioned again (step b).

These steps can be carried out individually, where appropriate with grinding beforehand. Milling should not, however, be carried out before coating a). It is also possible to carry out two or more of these variants—that is, identical or different variants—in succession.

The following embodiments of the process of the invention are conceivable.

In a first embodiment, one of steps a), b), and c) is performed a number of times (from 2 to 5 times) in succession.

In a second embodiment, steps a) and b) are carried out a number of times (from 2 to 5 times) in succession.

In a third embodiment, all steps a), b), and c) are carried out a number of times (from 2 to 5 times) in succession; in other words, the process is run through a number of times.

Process step b) is preferably carried out by heat treatment at 100–150° C. over the course of from 0.5 to 2 hours. After conditioning, the partly hydrophobicized silica present may have a methanol wettability of 20% or more. Fundamentally, a distinction may be made between wet and dry hydrophobicization.

Wet hydrophobicization means that the silicate starting materials are aqueous silica suspensions, silica feeds, or high water content silica filtercakes, which are coated with the corresponding hydrophobicizers, as described, for example, in DE 27 29 244 for precipitation suspensions with organohalosilanes.

Dry hydrophobicization means that the silicate starting materials are silica powders with different moisture contents of from 1 to 75%, which are coated with the corresponding hydrophobicizers. This process is described, for example, in DE 26 28 975.

The silica of the invention is prepared using organopolysiloxane derivatives; it is, however, also possible to use other silicone compounds which react to give organopolysiloxanes under the chosen reaction conditions (for example, dichlorodimethylsilane in an aqueous environment).

Preference is given to linear polysiloxanes having the composition SiRnXm(SiRxXyO)zSiRoXp (where 0≦n≦3, 0≦m≦3, 0≦x≦2, 0≦y≦2, 0≦o≦3, 0≦p≦3, 1≦z≦10000 with n+m=3, x+y=2, o+p=3) in which R is preferably represented by methyl.

Particular preference is given to polysiloxanes having the composition SiRnXm(SiRxXyO)zSiRoXp (where 0≦n≦3, 0≦m≦1, 0≦x≦2, 0≦y≦0.2, 0≦o≦3, 0≦p≦3, 1≦z≦1000 with n+m=3, x+y=2, o+p=3) in which R is preferably represented by methyl. Owing to the chosen process of the invention, however, it is specifically also possible to use polysiloxanes of low volatility which contain no functional groups.

Because of the presence of certain functional groups in organopolysiloxane derivatives, salts or low molecular mass substances such as NH3, amines, alcohols, etc. may be formed, which can lead to disruptive impurities. An important exception here is constituted by silanol-functionalized polysiloxanes, since the only impurity formed here is water, which is easy to remove under the chosen process conditions.

With preference, the hydrophobicizer may comprise a methyl-terminated polydimethylsiloxane, in particular one having a viscosity of 30–100 mPas, preferably 40–60 mPas. An example of a suitable polysiloxane oil is DOW CORNING (R) 200 FLUID 50 CS.

Since the aforementioned hydrophobicizers are compounds of low volatility, an important part in the initial distribution of the hydrophobicizers on the silica surface is played by capillary forces and diffusion events at the liquid/solid phase boundary.

Even if the hydrophobicizers used with preference exhibit a certain volatility in the course of a thermal treatment, the liquid/solid distribution is still important. For this reason, a distinction is made here between physical, initial distribution, conditioning, and heat treatment.

The heat treatment, i.e., process step c), is conducted at at least 300° C., preferably above 350° C., with very particular preference above 360–370° C., with an oxidizing gas. This gas can be air, Cl2, NOx (NO2, N2O5, NO, N2O), O3, O2, Br2, F2, or a mixture of these gases with further inert gases such as CO2, N2 or burner waste gases, in each case preferably at not less than 1% by volume.

Additionally, the oxidizing gas may optionally contain up to 80%, preferably up to 50%, with particular preference 20–40%, by volume of water.

In every case, a good gas throughput must be ensured; as far as possible, the gas must reach every silica particle. Apparatus suitable for ensuring this includes, for example, metal lattice ovens, muffle furnaces, or belt reactors.

In a muffle furnace, the bed height should be from 1 to 2 cm.

It is possible to combine two or more of these types of reactor. The process may be operated batchwise or continuously.

By way of example, the text below gives further details of the conditions in a belt reactor and in a muffle furnace.

Heat Treatment of a Granule Bed (in a Belt Reactor)

Heat treatment takes place with relatively high process gas throughputs (>5 m3/(h·kg), energy input via the process gases) through a bed of polysiloxane-treated silica. For this purpose, the silica must be granulated beforehand. Since the energy is supplied by way of the process gases, it is relatively easy to avoid local overheating here. Although the high process gas volumes result in a low concentration of crack products in the process gas, this does not result in poor hydrophobicization via the gas phase, since the concentrations of crack products in the granular pieces are much higher than between the granular pieces. Nevertheless, excess crack products can be expelled readily from the granular pieces, so that here as well it is possible to obtain high-whiteness products with optimum hydrophobicization. This reactor type can be operated safely at oxygen concentrations of 4–21%. Spherical granules are preferably of the order of 2–20 mm in size, while for rodlet-shaped granules widths of 2–20 mm and lengths of 2–40 mm are preferred. A bed of granles can be heat treated batchwise or continuously (in a belt reactor).

The preferred heat treatment times are 0.15–3.5 h at temperatures of 320–400° C., for a duration of 0.15–4 h.

When using this type of reactor, the heat treatment is typically followed by grinding of the granules.

Heat Treatment in a Muffle Furnace

The polysiloxane-coated silica is heat treated preferably in flat trays with a bed height of 2 cm. Heat treatment is carried out in air. The bed height selected firstly ensures a sufficiently high concentration of crack products in the interior of the bed (which permits effective hydrophobicization by means of the gaseous cleavage products), but secondly permits the unhindered escape of excess crack products.

Heat treatment in a muffle furnace may take place at 330–380° C. for a duration of at least 15 minutes but not more than 4 hours.

Following the conditioning step and/or heat treatment, the hydrophobicized silica is optionally ground. Milling before the coating step a), however, is not appropriate, and leads to low-grade products with inhomogeneous hydrophobicization.

The use of the precipitated silicas of the invention as a filler in silicone rubber formulations, in elastomer mixtures, polymers (e.g., PVC, polyurethanes), tires or sealants, as defoamer auxiliaries or as free-flow auxiliaries is likewise provided by this invention.

In order to develop fully their mechanical properties, silicone rubber formulations require active reinforcing fillers. It is common to use highly dispersed silicas. Because of the ease of mechanical processing of LSR (liquid silicone rubber) formulations, especially in injection molding processes, HTV (high temperature vulcanizing) silicone rubber formulations are increasingly being replaced by LSR mixtures. The reinforcing filler must bring about good mechanical properties in the vulcanizate without impairing the Theological properties of the silicone rubber formulations. After compounding, the silicone rubber formulations must be flowable and should not undergo afterstiffening even following prolonged storage times.

HTV and LSR formulations are processed at temperatures well above 100° C. At such temperatures, hydrous fillers may lead to disruptive formation of vapor bubbles in the silicone formulation. In the case of silicone rubber formulations which cure by atmospheric humidity, an excessively high water content in the filler results in unwanted curing in the course of storage. Accordingly, the water absorption characteristics, i.e., the amounts of water adsorbed at different relative atmospheric humidities, constitutes a measure of the processability of the filler.

The problem of vapor bubble formation occurs particularly with the hydrophilic precipitated silicas. Even hydrophobic precipitated silicas do not, typically, exhibit the low water absorption characteristics of the pyrogenic silicas.

The hydrophobic precipitated silica of the invention, however, exhibits water absorption characteristics comparable with those of pyrogenic silicas, is unaffected by discoloration, and also has low-thickening properties in silicone rubber formulations.

These properties are derived from the nature of the base silica used and from the nature of the hydrophobicization. The base silica is preferably a precipitated silica which has a very low silanol group density (the measure used for the silanol group density is the Sears number taken together with the BET surface area). The low silanol group density of the base silica is also manifested in a low loss on ignition of 3.0±0.5 at a BET surface area of about 160 m2/g.

For silicone rubber mixtures which are processed at temperatures of almost 200° C. with ingress of air, it is important that there are no organic constituents on the silica which might undergo discoloration under the influence of oxygen at these temperatures. Organosilicon compounds containing exclusively methyl, phenyl, fluorocarbon or hydrofluorocarbons as organic radicals are extremely temperature-stable even in the presence of atmospheric oxygen. In order, however, to achieve effective cleavage of the stable siloxane bridges of siloxane compounds and to bond them covalently to the silica, temperatures above 300° C. are required. At these high temperatures, siloxane compounds, especially in the case of precipitated silicas with a low silanol group density, normally lead to discoloration phenomena on the silica. The process of the invention makes it possible to suppress this discoloration. These discoloration phenomena are measured by reflectance measurements with an optical measurement technique based on diffuse reflection. Where the reflectances of silica are >94%, the silica-filled silicone rubber compound appears pure white. Since the refractive indices of silica and silicone rubber are close to one another, even very small impurities and discolorations in the silica filler become clearly visible in the silicone rubber. A reflectance of 93% already leads to a marked discoloration in the silicone rubber, visible with the naked eye, despite the fact that the silica powder before incorporation appears pure white to the viewer.

By mixing the silica of the invention with diorganopolysiloxanes and, where appropriate, further substances at room temperature or only slightly elevated temperature, it is possible to prepare compositions which can be cured to give elastomers, following the addition of crosslinking agents where appropriate. The silica of the invention has a low thickening effect, so that the compounds can be processed in LSR systems on injection molding machines. Mixing can be carried out conventionally, in mechanical mixers, for example.

The fillers used in accordance with the invention are employed preferably in amounts of from 1 to 50% by weight, more preferably from 10 to 40% by weight, based on the overall weight of the compositions which can be cured to give elastomers. In the case of HTV organopolysiloxane elastomers it is possible to use up to 50% by weight.

Besides diorganopolysiloxanes, the hydrophobicized precipitated silica of the invention, crosslinking agents and crosslinking catalysts, the compositions which can be cured to elastomers may of course where appropriate include fillers which are conventionally, often or usually, used in compositions that can be cured to elastomers. Examples of such substances are fillers having a surface area of less than 50 m2/g, such as quartz flour, diatomaceous earth, and also zirconium silicate and calcium carbonate, and also untreated pyrogenic silica, organic resins, such as polyvinyl chloride powders, organopolysiloxane resins, fibrous fillers, such as asbestos, glass fibers and organic pigments, soluble dyes, fragrances, corrosion inhibitors, agents which stabilize the compositions against the influence of water, such as acetic anhydride, agents which retard curing, such as benzotriazol, and plasticizers, and also trimethylsiloxy-endblocked dimethylpolysiloxanes.

The cited combination of physicochemical characteristics of the hydrophobic precipitated silica of the invention results in an outstanding reinforcing filler. The equilibrium moisture content, much lower than that of the known precipitated silicas, brings advantages in processing, in the context, for example, of vulcanization at atmospheric pressure, which produces pore-free vulcanizates in comparison with the use of the known, hydrated precipitated silicas. The optimized pH and the low DBP number lead to perceptibly reduced roller-softening times. The low electrolyte content in combination with the low moisture content leads ultimately to good electrical properties in the vulcanizates.

In silicone rubber sealants that cure by atmospheric humidity, the low water content of the hydrophobic precipitated silica of the invention gives advantages for the storage properties of the uncured sealants.

The examples which follow are intended to illustrate the present invention, without restricting its scope.

EXAMPLES

As the silicate starting material, it is preferred to use precipitated silicas which possess a very low silanol group density, i.e., a low alkali consumption/BET surface area ratio, a relatively high CTAB surface area for approximately the same BET surface area, and a high level of whiteness and purity.

Preparation of Base Silica

Aqueous sodium silicate solution (waterglass), and sulphuric acid is added with stirring into a reaction vessel pre-charged with water. During the addition, an alkaline pH is maintained. The silica precipitates from the reaction mixture, which is then acidified to pH 2–5 and filtered. The solid product is washed neutral with water and dried.

Any silica with the following properties is suitable as starting material for the hydrophobic process according to the invention.

BET surface area (m2/g)

50–170

CTAB surface area (m2/g)

50–170

Loss on ignition based on the substance dried 2 h/105° C.

≦3.5%

(DIN 55921) (%)

pH 5% (methanol/aqueous solution) (DIN 53200)

5–9

Conductivity (in 5% aqueous dispersion) (μS)

<500 μS

Tapped density (g/l)

>200 g/l

Sears Number

<13

The base silica and the polysiloxane are mixed until a defined carbon content is obtained; in other words, the mixing ratio is a function of the arithmetic proportion for setting the required carbon content.

1. Measurement Techniques

1.1 Methanol Wettability

Silicas whose surfaces have been modified with nonhydrolyzable organic groups are usually not wetted by water.

These hydrophobic silicas can, however, be wetted by a methanol/water mixture. The fraction of methanol in this mixture—expressed as a percentage by weight—is a measure of the hydrophobicity of modified silica. The higher the methanol fraction, the better the hydrophobicization of the substance.

Procedure

200 mg of each hydrophobic silica or silicate sample is weighed out into 6 centrifuge tubes each with a capacity of 15 ml, and each of the tubes is filled with 8 ml of a methanol/water mixture of ascending methanol concentration. The methanol concentration of the mixtures is guided by the anticipated methanol wettability. The centrifuge tubes are tightly sealed and then shaken vigorously (10 up-and-down motions). To separate the wetted silica/silicate fractions, the tubes are then centrifuged at 2500 rpm for 5 minutes. The wetted fractions form a sediment whose volume can be read off on the scale on the centrifuge tubes. On a graph, the sediment volumes are plotted against the methanol/water mixture concentration. These individual points produce a curve whose position and steepness characterizes the degree of hydrophobicization of the sample under analysis.

Apparatus:

Precision balance

Centrifuge

Centrifuge tubes, graduated

Dispensettes

1.2 DBP Absorption

The DBP absorption (DBP number), which is a measure of the absorbency of the precipitated silica, is determined as follows:

The dibutyl phthalate number is determined using the Brabender plastograph. The DBP number is a measure of the absorbency of a pulverulent product for liquid. The absorbency is dependent on the moisture content, the particle size, and the amount of material analyzed.

Apparatus and Reagents

Brabender plastograph with plotter

Multi-Dosimat E 415 (50 1) from Metrohm

Dibutyl phthalate

Procedure

12.5 g of silica are introduced into the kneader of the Brabender plastograph. With continued mixing (kneader paddle speed 125 rpm), dibutyl phthalate runs into the mixture at a rate of 4 ml/minute. The force required for incorporation is low. Toward the end of the determination, the mixture becomes poorly free-flowing. This fact is documented in an increase in the required force, which is indicated on the scale. When the scale has moved by 300, DBP metering is automatically shut off.

Evaluation

The density of DBP is 1.047 g/ml. The DBP absorption is based on the anhydrous, dried substance. When using precipitated silicas of relatively high moisture content, the value must be corrected using the following table if these silicas are not dried prior to the determination of the DBP number.

Correction table for dibutyl phthalate absorption - anhydrous -

% water

% water

% water

.0

.2

.4

.6

.8

0

0

2

4

5

7

1

9

10

12

13

15

2

16

18

19

20

22

3

23

24

26

27

28

4

28

29

29

30

31

5

31

32

32

33

33

6

34

34

35

35

36

7

36

37

38

38

39

8

39

40

40

41

41

9

42

43

43

44

44

10

45

45

46

46

47

The correction figure corresponding to the water content is added to the experimentally determined DBP value; for example, a water content of 5.8% would mean an add-on of 33 g/100 g for the DBP absorption.

1.3 Particle Size

The particle size is determined using a Malvern Mastersizer in ethanol following ultrasound treatment for 5 minutes. The measurement is made automatically and provides the average particle size d4.3 from a volume distribution.

1.4 Determination of the Tristimulus Value Ry in Accordance with DIN 5033

Application

Using the Datacolor 3890 spectrophotometer, the tristimulus value Ry is determined for silicas, silicates, and zeolites (powder suspensions).

Analytical Procedure

The silica to be analyzed is first ground to an average particle diameter of about 8 to 15 μm and then pressed to a tablet using a powder press. The amount required depends on the fineness of the powder. The amount of powder introduced is such that the thread of the press closure reaches its last turn.

The samples are placed under the meter, and whiteness measurement Ry and R460 are selected from the menu of the control computer. After the sample designation has been entered, the space key is operated in order to start the measurement.

Following entry of the memory code, the measurements are printed out.

The values are calculated automatically in accordance with the following formula:

y=∑400700⁢⁢S⁢(λ)*Y⁢(λ)*R⁢(λ)
where

Y(λ) is the standard distribution coefficient,

S(λ) is the relative spectral radiation distribution of the illumination source, and

R(λ) is the spectral reflectance of the sample.
1.5 Determination of the Sears Number of Silicas, Silicates and Hydrophobic Silicas

1. Application

Free OH groups are detectable by titration with 0.1 N KOH in the range from pH 6 to pH9.

4.2.8 The sample is titrated in the Memotitrator DL 70 in accordance with method S 911. If the course of titration is indistinct, a duplicate determination is carried out subsequently.
The Results Printed Out Are as Follows

pH

V1 in ml/5 g

V2 in ml/5 g
5. Calculation

V1=V*5EV2=V*5E

V1=ml KOH or ml HCl to pH6/5 g of substance

V2=ml KOH consumed to pH9/5 g of substance

E=initial mass
Principle

First of all the initial pH of the suspension is measured, then according to the result the pH is adjusted to 6 using KOH or HCl. Then 20 ml of NaCl solution are metered in. The titration is then continued to a pH of 9 using 0.1 N KOH.

10 g of the sample under analysis are weighed accurately to 0.01 g on the precision balance, and are introduced into the graduated 250 ml glass cylinder of the jolting volumeter. After 1250 jolts, the volume of the tapped material is read off.

Calculation

Tapped⁢⁢density⁢:⁢⁢g/1=E·1000I

E=initial mass in g

I=volume in ml
Apparatus

Precision balance

Engelsmann, Ludwigshafen

Jolting volumeter

250 ml glass cylinder,

Engelsmann, Ludwigshafen

graduated

Remarks

In special cases, the material may be passed through a 500 μm sieve before weighing, or the initial mass may be increased. This must be specified in a test report.

1.7 Determination of CTAB Surface Area

1. Application

The method is based on the adsorption of CTAB (N-cetyl-N,N,N-trimethylammonium bromide) on the “external” surface, which is also referred to as the “rubber-active surface”.

The adsorption of CTAB takes place in aqueous solution at pH=9 with stirring and ultrasound treatment. Excess, unadsorbed CTAB is determined by back-titration with SDSS (dioctylsodium sulfosuccinate solution) using a titroprocessor, the endpoint being given by the maximum clouding of the solution and determined using a phototrode.

For the calculation, an occupancy of 0.35 nm2 per CTAB molecule is assumed.

The determination is made in accordance with ASTM 3765.

With each measurement series, a standard sample of type VN 3 silica should be tested as well.

5.50 g of CTAB are dissolved with stirring (magnetic stirrer) in about 800 ml of warm (about 30–40° C.) demineralized water in a glass beaker, transferred to a 1l graduated flask, made up to the mark with demineralized water after cooling to 23–25° C., and transferred to a stock bottle.

Note

The solution must be stored and the measurement conducted at ≧23° C., since CTAB crystallizes out below this temperature. The solution should be prepared 10–14 days prior to use.

4.3 SDSS solution 0.00426 mol/l

1.895 g of SDSS (dioctylsodium sulfosuccinate) in a glass beaker are admixed with about 800 ml of demineralized water and the mixture is stirred with a magnetic stirrer until all of the material has dissolved. The solution is then transferred to a 1l graduated flask, made up to the mark with demineralized water, and transferred to a stock bottle.

SDSS solution readily undergoes biodegradation. The solution prepared should therefore be sealed well and should not be stored for more than 3 months.

The concentration of the CTAB solution is assumed to be exact: 0.0151 mol/l.

The concentration of the SDSS solution should be determined daily by means of a “blank” titration.
5. Procedure

5.2.5 Screw the titration vessel onto the titroprocessor and adjust the pH of the suspension to 9.0±0.05 using KOH, 0.1 mol/l

5.2.6 4-minute treatment of the suspension in the ultrasound bath

5.2.7 Filtration through a pressure filter fitted with a membrane filter.

During adsorption, it must be ensured that the temperature is held within the range from 23° C. to 25° C.

5.3 Titration

5.3.1 Pipette 5 ml of filtrate (see section 5.2.7) into 100 ml titration beakers and make up to about 50 ml with demineralized water

5.3.2 Screw titration beakers onto the titrator

5.3.3 Carry out titration with SDSS solution in accordance with the defined measurement method, until clouding reaches a maximum. Each titration should be performed as a duplicate determination; in the case where values do not agree, further titration should be carried out until the results are reproducible.
6. Calculation

re 5.2.4 Hydrophobic samples which are not wetted after stirring are to be dispersed carefully using an ULTRA-TURRAX before the pH is adjusted, in order to wet them.

re 5.2.5 For adjusting the pH it is advisable to use a titrator. The titration is carried out in accordance with the endpoint method.

re 5.2.7 For filtration, nitrogen from a gas bottle is to be used; an admission pressure of 4–6 bar is to be set.

re 6. Should it be necessary to repeat a measurement series, it should be noted in particular that the pH meter used to set the pH must also be recalibrated.
1.8 Determination of Water Vapor Absorption (Water Vapor Isotherms)

To determine the water vapor absorption, the sample is exposed to different relative humidities at constant temperature (30° C.). The establishment of a constant weight is awaited.

To start with, completely dry air (i.e., air humidity approximately zero) is used. After the equilibrium weight has been reached, this weight is chosen as the reference point; in other words, the water vapor absorption at a higher air humidity is expressed as the difference between the sample weight in completely dry air (following establishment of equilibrium) and the sample weight in humid air (following establishment of equilibrium). The air humidity is varied in steps of 10%.

In order to rule out hysteresis effects, both the water adsorption and the water vapor desorption are measured.

Example 1

50.0 m3 of water are charged to a reaction vessel. Slowly, 9.2 m3 of waterglass solution and 0.9 m3 of H2SO4 are added with stirring to the initial charge, an alkaline pH being maintained in the mixture during the addition. After the end of the addition of waterglass and H2SO4, the pH of the resulting suspension is within the alkaline range. The suspension is acidified and filtered, and the solid product is washed with deionized water. The hydrophilic base silica can be dried, preferably by an accelerated drying method. The following data relate to the dried precipitated silica thus obtained.

BET surface area (m2/g)

150–170

CTAB surface area (m2/g)

150–170

Loss on ignition based on the substance dried 2 h/105° C.

3 ± 0.5

(DIN 55921) (%)

pH 5% (methanol/aqueous solution) (DIN 53200)

6–7

Conductivity (in 5% aqueous dispersion) (μS)

<150

Tapped density (g/l)

>250

Sears number

<13

Example 2

The hydrophobic base silica was coated dry with silicone oil (methyl-terminated polydimethylsiloxane, viscosity 50 Pas, e.g., DOW CORNING (R) 200 FLUID 50 CS, carbon content about 33%) and conditioned by aging at room temperature for more than 48 hours (3 days) until it had obtained a methanol wettability of at least 20%. The material is heat-treated under oxidizing conditions in a muffle furnace with a bed height of not more than 2 m at a temperature above 330–360° C. for 1 h. The analytical data of the resulting material are given in Table 1.1.

TABLE 1.1

Product data, oxidatively heat-treated

Water

%

1.1

Loss on ignition

4.3

N2 surface area

m2/g

89

pH

7.9

Conductivity

μS

40

DBP

%

189

C content

%

3.9

Reflectance

%

95

Methanol wettability

%

67

Example 3

The base silica is coated with silicone oil (methyl-terminated dimethylpolysiloxane, 50 Pas, e.g. DOW CORNING (R) 200 FLUID 50 CS, carbon content approximately 33%) in a Gericke mixer in a mass ratio of 1:1. The resulting powder is conditioned for an hour at a temperature of 105° C. This produces a material in which, although it is wettable by water, the silica and silicone oil can no longer be separated from one another in water. Mixing of this masterbatch with filtercakes of the base silica produces stable formulations in which the silicone oil no longer separates from the hydrophilic filtercake. A hydrophobic masterbatch and a hydrophilic filtercake thus prepared (solids content about 20%) are conveyed together into the spin-flash drier, in which they are mixed (in a mass ratio of about 1:12) and dried. The dimethylsiloxane-treated silica is conditioned by aging at room temperature for at least 48 hours (about 3 days) until it has attained a methanol wettability of at least 20%. The analytical data of the conditioned silica are given in Table 2.1.

TABLE 2.1

Analytical data of the conditioned silica

Water

%

3.4

pH

6.3

Conductivity

μS

100

N2 surface area

m2/g

74

CTAB surface area

m2/g

119

DBP absorption

g/100 g

198

Tapped density

g/L

323

Reflectance

%

95.9

C content

%

5.03

Methanol wettability

%

>20

The conditioned precipitated silica is heat-treated under oxidizing conditions in a muffle furnace with a bed height of not more than 2 cm at a temperature above 330–360° C. for 1 h. The analytical data of the oxidatively heat-treated precipitated silica are given in Table 2.3.

TABLE 2.3

Product data, oxidatively heat-treated material

N2 surface area

m2/g

96

CTAB surface area

m2/g

41

Reflectance

%

94.5

C content

%

3.93

Methanol wettability

approx. %

67

Example 4

The initial distribution of silicone oil (viscosity of 50 Pas, methyl-terminated, e.g., DOW CORNING (R) 200 FLUID 50 CS, carbon content approximately 33%) on the silica (in the form of filtercakes) takes place in a spin-flash drier, with simultaneous drying. The dimethylsiloxane-treated silica is conditioned by aging at room temperature for at least 48 hours (about 3 days) until it has attained a methanol wettability of at least 20%. The analytical data of the conditioned silica are given in Table 3.1.

TABLE 3.1

Analytical data of the conditioned silica

Water

%

5.2

pH

6.1

Conductivity

μS

41

N2 surface area

m2/g

84

CTAB surface area

m2/g

132

Tapped density

g/L

317

Reflectance

%

95.9

C content

%

4.12

Methanol wettability

%

>20

The material is heat-treated under oxidizing conditions in a muffle furnace with a bed height of not more than 2 cm at a temperature above 330–360° C. for 1 h. The analytical data of the oxidatively heat-treated precipitated silica are given in table 3.2.

TABLE 3.2

Product data, oxidatively heat-treated material

N2 surface area

m2/g

102

Reflectance

%

94.7

C content

%

3.59

Methanol wettability

approx. %

67

Example 5

The base silica is coated in a mass ratio of 1:1 with silicone oil DOW CORNING (R) 200 FLUID 50 CS (dimethylpolysiloxane, 50 Pas, terminated with trimethylsilyl groups, carbon content approximately 33%). The resulting powder is conditioned for an hour at a temperature of more than 100° C. This produces a material in which, although it is wettable by water, the silica and silicone oil can no longer be separated from one another with water. Mixing of this masterbatch (i.e., 50% silica and 50% silicone oil) with aqueous silica dispersions produces stable suspensions in which the silicone oil can no longer be separated from the silica. The overall mixture typically contains 1 part by weight of silicone oil, about 4–8 parts by weight of silica, and 20–60 parts by weight of water. To prepare such a suspension, the masterbatch (i.e., 50% silica and 50% silicone oil) is mixed thoroughly with about 14–16 times the amount of filtercake (solids content approximately 20%) and about 11–13 times the amount of Table 4.1, those of the correspondingly conditioned silica in Table 4.2.

TABLE 4.1

Suspension data

Solids content

%

12.8

PH

5.2

Conductivity

μS

382

Viscosity

mPas

183

The suspension is dried using a spray drier. The dimethylsiloxane-treated silica is conditioned by aging at room temperature for at least 48 hours (about 3 days) until it has attained a methanol wettability of at least 20%. The analytical data of the conditioned silica are given in Table 4.2.

TABLE 4.2

Analytical data of the conditioned silica

Loss on ignition

%

12.4

Water

%

2.2

pH

6.4

Conductivity

μS

135

N2 surface area

m2/g

80

CTAB surface area

m2/g

131

DBP absorption

g/100 g

236

Tapped density

g/L

256

Reflectance

%

94.5

C content

%

4.21

Methanol wettability

%

>20%

The conditioned precipitated silica is heat-treated under oxidizing conditions in a muffle furnace with a bed height of not more than 2 cm at a temperature above 330–360° C. for 1 h. The analytical data of the oxidatively heat-treated precipitated silica are given in Table 4.3.

TABLE 4.3

Product data, oxidatively heat-treated

Water

%

0.6

N2 surface area

m2/g

91

CTAB surface area

m2/g

52

Reflectance

%

94.3

C content

%

4.01

Methanol wettability

approx. %

66

Example 6

Silicone oil, (polydimethylsiloxane, 50 Pas, e.g., DOW CORNING (R) 200 FLUID 50 CS, carbon content approximately 33%) is suspended in a suspension of the base silica (solids content 12.8%) using a high-shear mixer. The distribution of the silicone oil in the silica suspension is conserved by immediate spray drying. The dimethylsiloxane-treated silica is conditioned by aging at room temperature for at least 48 hours (about 3 days) until it has attained a methanol wettability of at least 20%. The analytical data of the conditioned silica are given in Table 5.1.

TABLE 5.1

Analytical data of the conditioned silica

Loss on ignition

%

13.0

Water

%

2.2

pH

5.5

Conductivity

μS

100

N2 surface area

m2/g

85

CTAB surface area

m2/g

137

DBP absorption

g/100 g

253

Tapped density

g/L

270

Reflectance

%

94.2

C content

%

4.78

Methanol wettability

%

>20%

The material is heat-treated under oxidizing conditions in a muffle furnace with a bed height of not more than 2 cm at a temperature above 330–360° C. for 1 h. The analytical data of the oxidatively heat-treated precipitated silica are given in Table 5.2.

TABLE 5.2

Product data, oxidatively heat-treated

Water

%

1.6

N2 surface area

m2/g

102

CTAB surface area

m2/g

43

Reflectance

%

94.2

C content

%

3.44

Methanol wettability

approx. %

65

The disclosure of the priority document, German Patent Application No. 101 38 490.4, filed Aug. 4, 2001, is incorporated by reference herein in its entirety.

Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.